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The impact of the polymeric matrix on the photophysical characteristics of monomeric dyes responsive to excited-state intramolecular proton transfer (ESIPT) was investigated through UV-Vis absorption as well as steady-state and time-resolved emission spectroscopies. For this purpose, two benzoxazole monomers (M1 and M2) with acryloyl groups at different positions in their molecular structures were employed to facilitate covalent bonding within a styrene chain. Our findings reveal significant variations in their excited-state properties due to the proximity of the acryloyl groups, which affects the energy barrier of the ESIPT reaction, the emission wavelength, and the balance between the normal and tautomeric forms. The experimental results were corroborated through theoretical investigations at the DFT/TDDFT level, specifically using the B3LYP-D3/def2-TZVP methodology. Three notable observations emerged: donor/acceptor groups at the meta/para positions induced electron distribution changes, causing red-shifted emission for M2; in the polymer film, particularly in PM1, intramolecular hydrogen bond deactivation favored N* emission over T* emission; and the zwitterionic character of the T* species. This study underscores the advantages of functionalization in polymers, which can lead to colorless films and prevalent N* or T* emission, and contributes valuable insights into molecular design strategies for tailoring the photophysical properties of polymeric materials.
RESUMO
In this study, we present the synthesis of benzimidazo[1,2-a] quinoline-based heterocycles bearing organosulfur and organoselenium moieties through transition-metal-free cascade reactions involving a sequential intermolecular aromatic nucleophilic substitution (SNAr). Both sulfur and selenium derivatives presented absorption maxima located around 355 nm related to spin and symmetry allowing electronic 1π-π* transitions, and fluorescence emission at the violet-blue region (~440 nm) with relatively large Stokes shift. The fluorescence quantum yields were slightly influenced by the chalcogen, with the sulfur derivatives presenting higher values than the selenium analogs. In this sense, the quantum yields for selenium derivatives can probably be affected by the intersystem crossing or even the photoinduced electron transfer process (PET). The compounds were successfully applied in all-solution-processed organic light-emitting diodes (OLEDs), where poly(9-vinylcarbazole) was employed as a dispersive matrix generating single-layer device cells. The obtained electroluminescence spectra are a sum of benzimidazo[1,2-a]quinolines and PVK singlet and/or triplet emissive states, according to their respective energy band gaps. The best diode rendered a luminance of 25.4 cdâ m-2 with CIE (0.17, 0.14) and current efficiency of 20.2 mcdâ A-1, a fivefold improvement in comparison to the PVK device that was explained by a 50-fold increase of charge-carriers electrical mobility.
RESUMO
Herein, we report the synthesis and characterization of two Pt(II) coordination compounds, the new platinum(II)[N,N'-bis(salicylidene)-3,4-diaminobenzophenone)] ([Pt(sal-3,4-ben)]) and the already well-known platinum(II)[N,N'-bis(salicylidene)-o-phenylenediamine] ([Pt(salophen)]), along with their application as guests in a poly [9,9-dioctylfluorenyl-2,7-diyl] (PFO) conjugated polymer in all-solution processed single-layer white organic light-emitting diodes. Completely different performances were achieved: 2.2% and 15.3% of external quantum efficiencies; 2.8 cd A-1 and 12.1 cd A-1 of current efficiencies; and 3103 cd m-2 and 6224 cd m-2 of luminance for the [Pt(salophen)] and [Pt(sal-3,4-ben)] complexes, respectively. The Commission Internationale de l'Eclairage (CIE 1931) chromaticity color coordinates are (0.33, 0.33) for both 0.1% mol/mol Pt(II):PFO composites at between approximately 3.2 and 8 V. The optoelectronic properties of doped and neat PFO films have been investigated, using steady-state and time-resolved photoluminescence. Theoretical calculations at the level of relativistic density functional theory explained these results, based on the presence of the Pt(II) central ion's phosphorescence emission, considering spin-orbit coupling relationships. The overall results are explained, taking into account the active layer morphological properties, along with the device's electric balance and the emitter's efficiencies, according to deep-trap space-charge models. Considering the very simple structure of the device and the ease of synthesis of such compounds, the developed framework can offer a good trade-off for solution-deposited white organic light-emitting diodes (WOLEDs), with further applications in the field of lighting and signage.
RESUMO
Speeding up the phosphorescence channel in luminescent copper(I) complexes has been extremely challenging due to the copper atoms relatively low spin-orbit coupling constant compared to heavier metals such as iridium. Here, we report the synthesis and characterization of three mononuclear copper(I) complexes with diimines, triphenylphosphine, and iodide ligands to evaluate the effect of the copper-iodide (Cu-I) moiety into the phosphorescence decay pathway. Temperature-dependent photophysical studies revealed combined thermally activated delayed fluorescence and phosphorescence emission, with a phosphorescence decay rate of the order of 104 s-1. Density functional theory calculations indicate very high spin-orbit coupling matrix elements between the low-lying states of these complexes. Compared to the classical [Cu(phen)(POP)]+, our results demonstrate that Cu-I is a versatile moiety to speed up the phosphorescence decay pathway in about one order of magnitude, and it can be prepared by a simplified synthetic route with few synthetic steps. Furthermore, the SOC matrix elements and the phosphorescence decay rates of these complexes are comparable to those of extensively applied coordination complexes based on heavier metals, making them a promising alternative as active layers of organic light-emitting diodes.
RESUMO
Multivariate Curve Resolution with Alternating Least Squares (MCR-ALS) was for the first time successfully used to evaluate an intricate photophysical behavior, where deprotonation on the electronic ground state (S0), intra and intermolecular proton transfer processes (ESPT and ESIPT) on the electronic excited state (S1) can simultaneously be presented. In this sense, the organic dye 2-(2'-hydroxyphenyl)benzothiazole (HBT) was used as a proof-of-concept model, where MCR-ALS showed to be a powerful tool for discriminate chemical reactions that occur concomitantly on different potential energy surfaces, which include photochemical reactions. As a result, the chemometric method showed to be a straightforward approach for the determination of the acidic strengths of those equilibria were estimated as 8.61 and 1.11 to hydroxyl deprotonation on electronic ground and excited states, respectively.
RESUMO
HYPOTHESIS: When tetradecyltrimethylammonium bromide, TTAB, is added to aqueous solution of sodium salicylate, NaSal, the threading of the aromatic anion into the micellar palisade leads to the formation of wormlike micelles. Based on the calorimetric titration of NaSal with TTAB, and on the lifetime of fluorescence of salicylate, we propose that the aggregation of the two components directly leads to the formation of wormlike micelles, without any pre-aggregation. EXPERIMENTS: By using an isothermal titration calorimeter, aliquots of TTAB were added to a dilute solution of NaSal. The energy involved in each addition was then integrated and the variation of enthalpy was determined. In the same range of concentrations and molar ratios, the surface tensiometry and time-resolved emission spectroscopy experiments were performed. FINDINGS: A very characteristic calorimetric signal associated with wormlike micelle formation was obtained, being the enthalpy variation of this process, ΔWLMH2980â¯<â¯0. When 1.2â¯mmolâ¯L-1 of NaSal is titrated with 11.0â¯mmolâ¯L-1 of TTAB at 298.15â¯K, ΔfH2980â¯=â¯-10.31â¯kJ per mol of injectant. By adding TTAB to NaSal solution, two fluorescence lifetimes of salicylate were observed solely after wormlike micelle being formed. The correspondent lifetime values of 4.0â¯ns and 7.2â¯ns are respectively associated with the free and associated species of salicylate. The new results demonstrated that wormlike micelles are the first aggregate formed when TTAB is added to salicylate. This aspect is relevant for understanding the mechanism of wormlike micelles formation.
RESUMO
A salicylidene derivative, N,N'-bis(salicylidene)-(2-(3',4'-diaminophenyl)benzothiazole) (BTS), reactive in the Excited State Intramolecular Proton Transfer (ESIPT) process, was synthesized and its photophysical properties were evaluated, presenting an emission covering the entire range of the visible spectrum. Due to its broad emission band, BTS was successfully tested as an active layer in solution-processed organic light-emitting diodes with white-light emission. These diodes were prepared using solution-based protocols with the dye solubilized in a poly(9-vinylcarbazole) matrix. Different guest : host (polymer : BTS) molar ratios were used to optimize the diode performance. The optimized architecture rendered the best so far all-solution-processed ESIPT OLED with a luminance of 34 cd m-2 at 13.5 V with CIE coordinates 0.31, 0.40.